Process for breaking petroleum emulsions employing certain oxyalkylation products ofreactive nitrogen containing compounds



PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING' CERTAIN OXYALKYLA- TION PRUDUCTS OF REACTIVE NITROGEN CONTAINING CDMPOUNDS Melvin De Groote, University City, and Kwan-ling Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application August 26, 1953 Serial No. 376,764

22 Claims. (Cl. 252-344) This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

Our invention provides an economical andrapid process for resolving petroleum emulsions of the waterin-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring Waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the invention.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Attention is directed to our oo pending applications Serial Nos. 305,079 (now abandoned) and 305,080 (now Patent No. 2,723,241, dated November 8, 1955), both filed August 18, 1952.

Application Serial No. 305,079 relates to a process of reacting a monomeric non-resinous nitrogen-containing compound having at least one active hydrogen atom and certain phenolic polyepoxides, therein described in detail.

Aforementioned co-pending application Serial No. 305,080, is concerned with the use of products of the kind described in Serial No. 305,079, for the resolution of petroleum emulsions of the water-in-oil type.

The present invention relates to a process for breaking petroleum emulsions employing a demulsifier including synthetic hydrophile products obtained by reacting a monomeric non-resinous nitrogen-containing compound having at least one active hydrogen atom and certain nonaryl hydrophile polyepoxides, hereinafter described in detail.

More specifically, our co-pending applications, Serial Nos. 305,079 and 305,080, filed August 18, 1952, employ certain glycidyl ethers of the kind described in U. S. Patent No. 2,500,499, dated March 14, 1950, to Bradley, and represented by the formula:

or cn-on F wherein R represents the divalent hydrocarbon radical of a dihydric phenol and n is an integer of the series 0, 1, 2, 3, etc. More specifically, such diglycidyl ethers may be illustrated by the following formula:

wherein n is an integer of the series 0, 1, 2, 3, etc.

2,819,223 Patented Jan. 7, .1958

In contradistinction to such diglycidyl ethers which introduce an essentially hydrophobe radical or radicals, the present invention is characterized by analogous compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but in fact are more apt to introduce hydrophile properties; Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contain less than 5 carbon atoms in an uninterrupted chain. For comparison, reference is made to polyepoxides, and more specifically diepoxides employed as the reactants in our copending applications, Serial Nos. 305,079 and 305,080, both filed August 18, 1952. Examples It is to be noted in this formula the terminal epoxy radicals are separated by the divalent hydrophobe group The diepoxides employed in the present invention are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending applications,

Serial Nos. 305,079 and 305,080, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature. See, for example, Italian Patent No. 400,973, dated August 8, 1951; see also, British Patent 518,057, dated December 10, 1938; and U. S. Patent No. 2,070,990, dated February 16, 1937, to Gross et al. Reference is made also to U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech. This particular last mentioned patent describes a composition of the following general formula:

2 lilalogen z in which 2: is at least 1, z varies from less than 1 to more than 1, and x and 2 together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the hydroxy groups thereof with the. epoxide ether groups of the above formula, and any remaining groups of the residue being free hydroxyl groups.

It is obvious from what is said in the patent that variants can be obtained in which the halogen is replaced by a hydroxyl radical; thus, the formula would become Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to dilferentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an amine as described. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation as, for example, kerosene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethyl ether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane(1,2-3,4 diepoxybutane) It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not ime-rent in the usual thermosetting resins. Note, for example, that said U. S. Patent 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin.

p y for purpose of illustration to show a typical diglycidyl ether of the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

6 BAH I HC-O-CH Commercially available compounds seem to be largely the former acyclic structure with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained an acyclic reactant having generally 2 epoxy rings as depicted in the next-to-last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine having a reactive hydrogen atom. Such amines may have a hydrogen atom attached to nitrogen or to oxygen.

To illustrate the products which are useful in the process 0f the present invention, reference is made to a reaction involving a mole of the diepoxide and a reactive amine. Proceeding with the example previously described it is obvious the reaction ratio, for example, 2 moles of amine and one mole of the diepoxide, gives a product which may be indicated as follows:

in which n is a small whole number less than 10, and usually less than 4, and including 0, and R represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water or, for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether one or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents the anhydro base or the free base (combination with water), or a salt form such as the ace tate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from relation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serve to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly soluble in 5% acetic acid, or gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of distilled water at ordinary nitrogen atoms present or a repetitious ether linkage as in the case of oxyethylated or oxypropylated monoamines or polyamines.

Speaking of oxyethylation and oxypropylation, it goes without saying that all of the products obtained from any of the nitrogenous containing reactants are in turn again oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, derivatives can be obtained by use of a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

The products obtained as hereinafter described may vary from soluble nitrogen-containing compounds which, in fact, are comparatively simple diamines for example, to products which enjoy insolubility due to cross-linking, increased molecular size, or the initial presence of large hydrophobe groups. The product as obtained by the procedure herein described may, of course, be an intermediate which is subjected to reaction with an acylation reagent, such as a higher fatty acid or with an alkylene oxide which either may provide increased hydrophile efiect in the case of ethylene oxide, glycide, or the like, or perhaps increased hydrophobe efiect in the case of propylene oxide, butylene oxide, phenylethylene oxide, etc. However, for the specific purpose of demulsification it is our preference that the product be surface-active. It is generally understood that surface-activity is due to a modification of properties of the surface layer between two phases in contact with each other.

Thus, as far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxyacetate, have sutficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene-glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

The same test will serve to identify products having emulsifying power and, thus, is an indication of surfaceactivity. It will be noted that in a subsequent table describing examples a comparatively large number of examples are so selected to exhibit this particular property. Reference to emulsifying property includes the property of the anhydro base as such or the free base which is the hydrated form, or a salt of a low molal acid, such as acetic acid, hydroxy-acetic acid, or gluconic acid. It will be noted that for most purposes the most desirable derivative is obtained by reaction involving 2 moles of the amine and one mole of the polyepoxide, and particularly diepoxide.

For purpose of convenience, what is said hereinafter will be divided into four parts.

Part 1 is concerned with the hydrophile non-aryl poly- Part 4 is concerned with the resolution ofpetroleuin emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No. 2,070,990, dated February 16, 1937 to Groll et al.; and U. S. Patent No. 2,581,464, dated January 8, 1952 to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

CH2 CH CHllOOH2 0HGH2 Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula:

H2o ooH2oH2o- 3Hz CH3 CH3 The diepoxides previously described may be indicated by the following formula:

H It R H HC-O[R C CH in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral 0 or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH CH and n is 1. In another example previously referred to R is CH OCH and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. The particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal "7 oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. '50 presented the formula becomes:

In the above formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which or more carbon atoms are united in a single uninterrupted group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol OHROI-I must be watersoluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by H H H -C-COH Thus, R(OH),,, where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides it actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula in which R is C H (OH) it is obvious that reaction with another mole of cpichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the approximate diepoxide. The molecular weight is approximately 370 and the number of, epoxide groups per molecule are approximately 2.

For this reason in the first ofsa' series of subsequent ex-v 8 amples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quatities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to difierentiate from comparable aryl compounds is to use the terminology epoxyalkanes and. more particularly, polycpoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a. heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

See Canadian Patent No. 672,935.

PART 2 As previously noted, Part 2 is concerned with the amino reactants employed in conjunction with the polyepoxide reactant usually containing two oxirane rings. Since the reactant described in detail in Part 1, preceding, is essentially an oxyalkylating agent it is obvious that any amino compound, and more broadly any nitrogen-containing compound such as an amide, which is oxyalkylation susceptible is suitable for the present purpose. in essence, this means that the product must have a labile hydrogen attached to either oxygen or nitrogen. Such hydrogen atom may be attached directly to a nitrogen atom as in the case of an amide, an amine, or the like. However, it may be attached directly to oxygen as in the case of triethanolamine; or a labile hydrogen atom in the form of a hydroxyl group may appear in the acyl radical of an amide or the ester of an amine, such as an ester of etha noldiethyl amine; although ricinoleic acid exemplifies an acyl radical with a hydroxyl group which is somewhat reactive, yet more satisfactory, is a hydroxy carboxylic acid such as wherein R is a six-sided carbocycle of the formula C H as described in U. S. Patent No. 2,457,640, dated December 28, 1948, to Bruson et al. 7

One need not necessarily use monoamino compounds or compounds containing a single nitrogen atom but may use polyamino compounds including, of course, compounds where there is more than one amide group. There is no limitation as to the group which is attached to the nitrogen atom insofar that it may be alkyl, aryl, alicyclic, and alkylaryl, arylalkyl, etc. Heterocyclic compounds such as morpholine may be employed. The amino compound or amidocompound maybe water-soluble -or water-insoluble. The amine may contain a phenolic hydroxyl as, for example,

R CHgNH,

where R is an alkyl group generally having five carbon atoms or more. See U. S. Patent No. 2,410,911, dated November 12, 1946, to Wasson et al. Further examples appear in the subsequent text.

Needless to say, since it is specified that the amino compound or amido compound be oxyalkylation susceptible it can be subjected to reaction with some other alkylene oxide than the instant reactant containing the two oxirane rings, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycide, glycidyl ethers of methanol, ethanol, propanol, phenol, and the like. The fact that such reactants are oxyalkylation susceptible means they are also susceptible to reaction with imines, such as ethyleneimine, propyleneimine, etc. Furtherfore, any non-nitrogenous compound which is oxyalkylation susceptible, for instance, an alcohol or a phenol, may be reacted with ethylene-imine to give suitable compounds to be employed as reactants in the present procedure. See,

for example, U. S. Patent No. 2,318,729, dated May 11,

1943, to Wilson. This same procedure, of course, described in said Wilson patent can be used in conjunction with any alcohol or phenol. Indeed, water-soluble polymers of lower alkylene imines can be employed. See U. S. Patent No. 2,553,696, dated May 22, 1951, to Wilson.. The imines may have ether linkages as previously noted. See, for example, the products described in U. S. Patent No. 2,325,514, dated July 27, 1943, to Hester.

As is obvious from what is said, one need not use organic compounds but inorganic compounds such as ammonia or hydrazine can be employed. In the case of amides, one is not limited to the amides of monocarboxy or polycarboxy acids but one may use sulfonamides or the amide of carbonic acid, i. e., urea. However, certain derivatives of urea appear more satisfactory than urea itself. See U. S. Patent No. 2,352,552, dated June 27, 1944, to Kienzle.

As to a variety of sulfonamides which are readily susceptible to oxyalkylation, particularly with ethylene oxide or propylene oxide, see U. S. Patent No. 2,577,256, dated December 4, 1951, to Lundsted. Such sulfonamide could be used as such or after treatment with one or more moles of ethylene oxide, propylene oxide, etc.

For purpose of convenience attention is directed to a sizeable number of nitrogen-containing compounds which are available in the open market as differentiated from those which could be readily prepared by reaction with ethylene oxide, propylene oxide, ethyleneimine, etc. In some instances even these reactants, notwithstanding the fact that they do have a labile hydrogen atom, are more satisfactory after treatment with ethylene oxide so as to have the labile hydrogen atom attached to oxygen instead of nitrogen.

Amine 220 (Carbide and Carbon Chemicals Company,

New York city, N. Y., designation for Amine 803 (Carbide and Carbon Chemicals Company,

New York city, N. Y., designation for Ethyl amine Diethyl amine Isopropyl amine Diisopropyl amine n-Butyl amine Dibutyl amine V N-acetyl ethanolamine N,N-diethyl ethylene Tetraethylene pentamine Propylene diamine N-hydroxyethyl propylene diamine diamine Monoisopropanolamine N,N'-dihydroxyethyl Diisopropanolamine ethylene diamine Triisopropanolamine Dimethyl isopropanolamine Dibutyl isopropanolamine 1,3-diaminopropane 2,5-dimethyl piperazine Morpholine N-hydroxyethyl morpholine N-aminoethyl morpholine N-aminopropyl morpholine 1,3-diaminobutane Di-n-amylamine Sec-amylamine Diethyl ethanolamine 2-amino-4-methylpentane 4-amino-2-butanol l-dimethylamino-Z- N-butyl diethanolamine propanol Aminoethyl ethanolamine S-isopropylamino-l-penta- Di (Z-ethylhexyl-ethanolnol amine Tetraethanol ammonium hydroxide N-butylaniline High molecular weight aliphatic amides known as Armid 8, Armid 10, Armid 12, Armid 14, Armid 16, Armid 18, Armid HT, Armid R0, Armid T, Armid TO and Armid C, described in a chemical phamplet entitled Armids, issued by Armour Chemical Division, Chicago 9, Illinois.

Similarly, secondary high molecular weight aliphatic amines known as Armeen 2C and Armeen 2HT, as

described in circular entifled Secondary Armeens, as'

issued by Armour Chemical Division, Chicago, Illinois.

Also, high molecular weight aliphatic amines known as Armeen 10, Armeen 16D, Armeen HTD, Armeen 18D, and Armeen CD, as described in a pamphlet entitled Armeens, issued by Armour Chemical Division, Armour and Company, Chicago, Illinois.

Included also are fatty diamines having both primary and secondary amine groups and sold under the name Duomeens, such as Duomeen T, as described in a circular entitled Duomeen T issued by Armour Chemical Division, Chicago, Illinois.

Other suitable amines are primary monoamines of the type H(OC H ),,NH where 21:3 to 5.

Suitable amines having an aromatic ring include alphamethylbenzylamine, alpha methylbenzylmonoethanolamine and alpha-methylbenzyl diethanolamine.

One may use tertiary alkyl' primary amines such as tertiary-octylamine, alkylamine 81-R, alkylamine 8l-T, alkylamine JM-R, and alkylamine JM-T. As to a description of these amines see Rohm & Hass Company, Philadelphia, Pa., Primary Amines.

Other amines include:

-4-amino-l,3-butanediol 3-diethylaminopropylamine v pamphlet entitled Tertiary-Alkyl.

11 4,4-dimethyl-1,3-butanediol 2-amino-1,4-butanediol 3-amino-1,4-butanediol 1-amino-2,3butanediol Tris-(hydroxy methyl) amino methane An additional desirable group of amines are dialiphaticaminoalkylcardanols, and particularly those having 10 to 40 carbon atoms in the dialiphatic grouping; examples include di-2-ethylhexylaminomethylcardanol, diamylaminomethyl cardanol, dilaurylaminomethyl cardanol, and di-n-butylaminomethyl cardanol. See U. S. Patent No. 2,489,672, dated November 29, 1949, to Revukas.

Further examples of this same type of material and which has available both a phenolic hydroxyl and an alkanol hydroxyl is illustrated by the condensation product derived from a phenol, either monofunctional or difunctional, such as para-tertiary butylphenol, para-tertiary amylphenol, octylphenol, nonylphenol, and similar phenols having a substituent such as two 'butyl groups or two nonyl groups in both an ortho and the para position. Such phenols are reacted with an aldehyde, such as formaldehyde, acetaldehyde, etc. and an alkanol phenol, such as diethanolamine, ethylethanolamine, dipropanolamine, and other amyl amines having only one amino hydrogen atom. See, for example, U. S. Patent No. 2,457,634, dated December 28, 1948, to Bond et al.

Amines having ring structures of course include aniline, diphenylamine, cyclohexylamine, dicyclohexylamine, and various comparable amines with alkyl substituents in the ring and similarly such amines after treatment with ethylene oxide, propylene oxide, glycide, etc.

It is to be noted, of course, that the above description in the text immediately preceding is largely miscellaneous in character because the reference is to products available in the open market. Practically every amine which is oxylkylation susceptible is also acylation susceptible although there are some compounds, such as amides, sulfonamides, urea, etc., which are much more readily oxyalkylation susceptible than acylation susceptible for the reason that it is much more difficult to form a secondary amide, and more especially a tetriary amide, than it would be to react a primary amide with one or more moles of an alkylene oxide.

However, U. S. Patent No. 2,571,119, dated October 16, 1951, to De Groote et al., covers essentially the same compounds herein proposed, including imidazolines and oxylkylated imidazolines. This patent divides the nitrogen compounds into a number of classes which is convenient, when one considers the reactions dis-cussed in Part 3, succeeding. What is said immediately hereafter is substantially the text verbatim as it appears in that patent with only the obvious change in the few introductory sentences.

Nitrogen-containing compounds which are oxyalkylation susceptible can be divided into various classes as to their structure. As has been pointed out, reactivity towards such alkylene oxides having a reactive ring, such as the oxirane ring, generally means the presence in them of either an amino nitrogen atom, amido nitrogen atom, or an alkanol radical or a phenolic radical, or the equivalent, that is, hydrogen attached to nitrogen or oxygen. In the following five classes the amides, sulfonamides, ureas, etc., are omitted but suitable reference has been made to these previously. The inorganic nitrogen compounds include ammonia, hydrazine, etc. The organic nitrogen compounds include amines, such as primary, secondary and tertiary amines, polyamines as well as monoamines, amines containing alkanol radicals or the equivalent, and amines which contain both a reactive hydrogen atom attached to oxygen and one or more reactive hydrogen atoms attached to nitrogen. For purpose of convenience the nitrogen-containing compounds employable as reactants here are divided into the following classes.

to produce secondary amides.

' no-2-butanol-1-dimethylamino-2-propanol,

amino-l-pentanol, etc. The high-molal monocarboxy acid.

Class L-Animonia and hydrazine and compounds containing only one nitrogen atom per molecult with at least one reactive hydrogen atom attached thereto, but in the absence of reactive hydroxyl groups. Primary amines like ethylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, decylamine, tetradecylamine, hexadecylamine, and octadecylamine are members of the class. High molal primary amines, like those sold by Armour & Company, Chicago, as Armeens, usually with a figure designation showing the numbers of C atoms in the alkyl radical, e. g., Armeen 10, Armeen 12, Armeen 16, etc., are included. So are secondary amines like diethylarnine, dipropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, etc. Also included are aniline, cyclohexylamine, bis'(dimethylbutyl)-amine, 1-3-dimethylbutylarnine, 2- amyl-4-methyl pentane. Amides are also included in this class, but are commonly not attractive for use here because of the difliculty of securing satisfactory reaction Other useful amines of this class will be suggested by the above-recited list.

Class 2.--Compounds containing only 1 nitrogen atom per molecule, but in which a hydroxyl group is the only reactive and functional group, as here employed. in this class are tertiary alkanolamines like diethylethanclamine, dimethylethanolamine, triethanolamine, diethylpropanolamine, methyldiethanolamine, ethyldipropanolamine, phenyldiethanolamine, etc. The products obtained by reacting such amines with alkylene oxides like ethylene oxide or propylene oxide are also useful, e. g., triethanolamine may be reacted with ethyleneor propylene oxide. Alkyl primary amines, particularly those in which the alkyl group originates in fatty materials and contains from about 10 to about 18 carbon atoms, may be treated with such alkylene oxides to produce useful nitrogen compounds of the generic formula, Rdi(Alkoxy)nH-N. Similarly, amides of the generic formula RCONH may be oxyalkylated to produce compounds of the generic formula,

(Alkoxy),,H

RCON

(Alkoxy)..H The ricinoleyl amides of dialkylamines are also examples of this class. Other examples of similarly useful reactants of this class will be suggested by the above list.

Class 3.Compounds containing only 1 nitrogen atom per molecule and having, in addition to at least 1 reactive hydrogen atom attached thereof, also at least 1 reactive hydroxyl group. in this class are included monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, ethylethanolamine, propylethanolamine, ethylpropanolamine, phenylethanol-amine, 2amino-2- methyl-l-propanol, 4-amino-4-methyl-2-pentanol, 4-ami- S-isopropylamides of monoalkanolamines are also examples of this class. Obvious equivalents will be suggested by the above list.

Class 4.Esters of tertiary alkanolarnines having only 1 nitrogen atom per molecule, to which nitrogen atom' there are attached no reactive hydrogen atoms, but in which ester molecule there is at least 1 reactive hydroxyl radical, either attached to the nitrogen atom through a suitable divalent radical or else as a part of the acyl radical present in said ester. The acyl radicals are those found in monocarboxy acids having 8 C atoms or more. Examples of this class of nitrogen compound are the esters produced from oleic acid and ethyldiethanolamine or from ricinoleic acid and diethylethanolamine. In the case of the above oleic esters, esterification consumes only one of the two hydroxyl groups originally present in that alkanolamine, leaving one such reactive hydroxyl group in the ester, for use for the present purpose. the case of the ricinoleic ester above, esterification com sumes the only hydroxyl group originally present in the alkanolamine used; but the ricinoleic radical itself contains a reactive hydroxyl group, and the ester is therefore still reactive for the present purpose. In preparing the compounds of this kind, there may be employed only as many acyl radicals as there are alkanol radicals, less one; except that, if the acyl radical itself retains at least one reactive hydroxyl group after esterification, then one may use as many acyl radicals as there are alkanol radicals. Examples of suitable alkanolamines have already been recited under Class 2 above; but some of the examples there recited will not serve here in all cases because they contain only one reactive hydroxyl group and this is destroyed in esterification. If ricinoleic acid is the acylating reactant, all those recited there are useful here. It is apparent from the foregoing description that the intent is to retain at least one reactive hydroxyl group in the ester prepared from the tertiary alkanolamine and the acylating reactant employed.

Class 5.Cmpounds which are non-resinous, which contain more than 1 nitrogen atom per molecule, and which contain no acyl group. Examples include the alkylene polyamines like ethylenediamine, diethylenetriamine, triethylene-tetramine, tetraethylenepentamine, propylenediamine, dipropylenetriamine, etc. These alkylene polyamines may be treated with an alkylene oxide like ethylene oxide or propylene oxide to produce derivatives which are also useful here, such as hydroxyethylethylenediamine, tetraethanoltetraethylenepentamine, etc. Oxyalkylation may be continued, of course, until a considerable number of alkyleneoxy groups have been introduced, without adversely affecting the utility of such derivatives here. Imidazolines, both monoimidazolines and di-imidazolines, are included in this present class. Such compounds may be prepared by reacting, under sufficiently severe conditions, a monocarboxylated acid and an alkylenepolyamine. For example, when oleic acid and tetraethylenepentamine are reacted in molar proportions at a temperature somewhat exceeding 200 C. amidification first occurs, with the elimination of 1 mole of water. On continued heating, especially at temperatures approaching 300 C. a second molecule of water is split out, the acyl group becomes an alkyl group, the imidazoline ring is formed, and the product is the monooleyl imidazoline of tetraethylenepentamine. If the proportion of fatty acid is doubled, a dioleyl imidazoline is produced, instead. Examples of such mono and di-imidazolines are recited and described in U. S. Patents Nos. 2,466,517 and 2,468,163, dated April 5, 1949, and April 26, 1949, respectively, to Blair and Gross. Furthermore, U. S. Patent No. 2,369,818, dated February 20, 1945, to De Groote and Keiser, illustrates the fact that such imidazolines may be subjected to reaction with an alkylene oxide like ethylene oxide, to produce oxyalkylated derivatives thereof which are useful here.

Other examples of suitable reactants of the present class include 3-diethylaminopropylamine, l-3-diaminobutane, trigylcoldiamine, and the compound, NH (CH O(CH O(CH NH See U. S. Patent No. 2,552,530, dated May 15, 1951, for additional examples of suitable nitrogen compounds of this class.

Class 6.Compounds containing more than 1 basic nitrogen atom per molecule, and which also contain at least one high molal acyl group. The amides produced from monocarboxy acids like the fatty acids and alkylene polyamines like tetraethylenepentamine, and referred to in Class above as being intermediates formed in the preparation of certain imidazolines, are representative of this class. For example, if one reacts 1 mole of oleic acid with 1 mole of tetraethylenepentamine until 1 mole of water of reaction is removed, the product is an amide of the present class. Stearic acid or tall oil or other detergent-forming acid having at least 8 C atoms may be substituted for oleic acid in producing such an amide, with equally satisfactory results. Other alkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc., may be substituted for tetraethylenepent amine in the examples just discussed, to produce desir-. able amides. 0r such polyamine may be oxyalkylated prior to use in the amidifica-tion reaction, using ethylene oxide or propylene oxide. If imidazolines of the kind included in class 5, immediately above, are acylated, such acylated imidazolines are then properly included in the present class of nitrogen compounds. Other useful examples of nitrogen compounds of the present class are described in U. S. Patent No. 2,243,329, dated May 27, 1940, to De Groote and Blair.

Of all the members of this sixth class of nitrogen compounds, we prefer to employ as reactants here a type of product which is related to the esters of Class 4 above. If, instead of using molal proportions of high molal monocarboxy acid having 8 carbon atoms or more and of tertiary alkanolamine, as in the preparation of materials of Class 4, above, one employs 2 or more moles of alkanolamine for every mole of monocarboxy acid, desirable reactants of the present class are formed. These may be termed acylated polyaminoalcohols. To describe more precisely this particular and preferred type of Class 6 nitrogen compounds, the following statement is made.

The compounds are acylated derivatives of a basic polyaminoalcohol of the formula:

RI! mo Rona said acylated derivatives thereof being such that there is at least one occurrence of the radical RCO, which is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R is a member of the class consisting of aminoalkanol radicals, and polyaminoalkanol radicals, in which polyaminoalkanol radicals the amino nitrogen atoms are united by divalent radicals selected from the class consisting of alkylene radicals, alkyleneoxyalkylene radicals, hydroxyalkylene radicals, and hydroxyalkyleneoxyalkylene radicals, and all remaining amino nitrogen valences are satisfied by hydroxyalkyl radicals, including those in which the carbon atom chain is interrupted at least once by an oxygen atom; R is an alkylene radical having at least 2 and not more than 10 carbon atoms; n is a small whole number varying from 1 to 10; and RC0 is a substituent for a hydroxyl hydrogen atom.

In the foregoing formula, R may, in some of its multiple occurrences in the molecule, represent the same alkylene radical or it may represent different alkylene radicals, so long as each R contains from 2 to 10 carbon atoms. For example, oxyethylated, oxypropylated triethanolamine would contain some R radicals which are C H radicals, and others which are C l-I radicals.

Further description of the acylated poylaminoalcohol reactant will be found, for example, in U. S. Patent No. 2,470,829, dated May 24, 1949, to Monson.

It is to be understood that isomeric forms of the nitrogenous compounds of all 6 classes above may be employed instead of the forms referred to above, without departing from the invention.

Other amines, some of which are predominantly hydrophile and some of which are predominantly hydrophobe, also may be employed. Reference is made to previously mentioned U. S. Patents Nos. 2,181,929, 2,330,222, 2,356,565, 2,396,097 and 2,552,530. Examples of hydrophile amines include glucamine and maltosamine.

Particular reference is made to aforementioned U. S. Patent No. 2,552,530, for the reason that it illustrates suitable amines in which the molecular weight may be as high as 4,000 to 10,000. Other amines may be obtained in a comparable fashion from monoamines as raw materials instead of polyarnines as, for example, from triethanolamine. Similarly, types of materials can be obtained which are extremely hydrophile by oxyalkylation in the same manner using ethylene oxide or glycide. Generally speaking, however, it is our preference that the nitrogen-containing reactant has a molecular weight of less than 3,000 and generally less than 1,800.

PART 3 As has been pointed out previously, the reactions involved are essentially oxyalkylation reactions involving a nitrogen-containing compound (non-resinous) having at least one labile hydrogen atom.

If one employs a compound such as methylamine ammonia, which is a gas, the oxylkylation procedure can be conducted in equipment of the kind which has been described for oxyethylation, except that the procedure is reversed in that the diglycidyl ether as such is dissolved in inert solvent with or without an added catalyst, such as 1% of sodium methylate, and is reacted by slowly passing in the reactive nitrogen-containing reactant, to wit, methylamine. However, the most important phase of the instant invention is concerned with organic nitrogen derivatives which are invariably solids or liquids as distinguished from gases. Therefore, the reaction with the oxyalkylating agent, i. e., the diglycidyl ether or, in any event, the polyepoxide reactant as described, in conducted in an ordinary reaction vessecl which need not have the usual modifications necessary when a gas, such as ethylene oxide, is used. Indeed, the reactions can be conducted readily in glass laboratory equipment such as the kind used for resin manufacture as described in a number of patents, as, for example, aforementioned U. S. Patent No. 2,499,365. All that is necessary is to put the reactants together and note whether the reaction goes without the presence of a catalyst. Generally speaking, if there is a basic nitrogen atom present reaction will take place. If the reaction does not take place, or takes place too slowly, then one need only repeat the experiment using a small amount of catalyst, for instance, about one, two or 3 percent of sodium methylate, or finely divided caustic soda. Any of the usual oxyalkylation catalysts can be employed. For obvious reasons, a basic catalyst is most desirable.

If the reaction proceeds too rapidly and an insoluble rubbery mass is obtained, the best procedure is simply to repeat the preparation with greater care and stop just short of the incipient gelation point and then determine if the reaction has gone to completion, or substantially so. In some instances when a reactant yields rubbery masses rather readily and there is no other objection to so doing, one is well advised to react the nitrogenous reactant with one or more moles of ethylene oxide and then use the oxyethylated derivative instead of the initial nitrogencontaining compound. As is also known, gelation often can be prevented by introducing some other group, such as a cyclohexyl group, a phenyl group, or a long-chain aliphatic group at a point where possibly there are two reactive groups immediately adjacent, as in the case of the primary amine. Actually, the choice of reactants is so Wide and so diverse that this probably presents no real or additional difiiculty in the overwhelming majority of cases.

For purpose of convenience, the following examples are included in tabular form in Table I. In these examples two reactants have been used, to wit, diepoxide A (or diglycidyl ether A) and diepoxide B (or diglycidyl ether B) as described in Part 2, preceding. In the following table the ratio was two parts of the amine compound and one part of the diepoxide. Under other circumstances other ratios can be used as indicated elsewhere.

TABLE I Time of Max. Solubility Ex. Reaetants Catalyst reaction temp., Color and physical state No. (NaOCLEh) (hrs.) 0.

Water 5% HOAC Xylene Diphenylarnine, 84.6 g.+A, 92.5 g No 2 190 Dark liquid Partly Disperslble Soluble.

persi e. Benzylarniue, 53.6 g.+A, 92.5 g. No 2 185 Yellow semisolid Dispersible.--- Partly soluble. Arrneen 8-D, 133 g.+A, 185 g. No 1. 5 190 Light brown semisolidd Soluble. Arrneen 10-D, 185 g.+A, 185 No 1. 5 190 do D0- Armeen 12-D, 10 g.+A, 92.5 g No 1. 5 190 Red semisolid.. Do. Armeen 14-1), g.+A, 92.5 g No 1. 5 195 Brown semisolid. D0. Armeen 16-D, 126 g.+A, 92.5 g No 1. 5 192 .do D0. Armeen 18-D, 13S g.+A, 92.5 g No 1 200 Light brown waxy solid Do. Primene 81T,108.5 g.+A, 9 No 2. 5 Dark brown semisolid D0. Primene JIM-T, 172 g.+A, 9 No 2 200 Red brown semisolid Do. Rosin Amine D, 157.5 g.+A, No 1.5 190 Red brittle so1id D0- Duornoen 12, 151.5 g.+A, 92.5 No 2 175 Dark brown semisolid- D0. Duorneeu C, 160.5 g.+ 92.5 No 2 170 Dark semisolid 0- Duomeen S, 201 g.+A, 92.5 No 2 160 Brown semisolid. Do. Duomeen T, g A .5 No 2 150 Light; brown semisoliddo Do. Arrnid 10, 8 1. S 2 210 Green gray solid Partly dls- Do.

persible. persible. Armid 14, 6 1. 2 1 250 Dark brown solid 0 ..d0 D0- Armid 16, 7 1. 3 1 Disperslble. Armld HT, 8 1. 4 l uble. Ethorneen C No 1. 5 Do. Ethomeen 0/2 No 1. 5 Do. Ethomeen 18/2 No 1. 5 D0. Ethomeen18/25, 9 No 1.5 do D0- Ethomid HUT/l5, 9. 1.1 4 Soft yellow solid persible. Ethomid HT/25, 75 g.+A, 14.8 g.. 0.9 4 220 Soft brown solid Soluble 0- Ethomid I-IT/60, 74.4 g.+A, 5.6 g. 0. 8 4 265 Ethomid RO/25, 75.4 g.+A, 14.8 g 0.9 4 220 Brown semisolid do DO. Furlurylarnine+propylene oxide No 2 195 Dark brown liquid Dispersible D0- 1:17.9, 113.5 g.+A, 18.5 g. Furiurylamine+propylene oxide N0 2 200 do 1:30.5, 186 g.+A, 18.5 g. Furt'ury1arnine+propylene oxide No 2 190 do D0- 1:51.8, 155 g.+A, 9.5 g. 3L Triethanolamine+propylene oxide No 3 do do d0 0.

1:27, 171.5 g.+A, 18.5 g. 32- Triethanolam1ne+propylene oxide No 3 200 do do do D0.

1:302, g.+A, 18.5 g.

'I he Duomeens are fatty diamines of this general for mula:

. The Armids are, as stated, high molecular weight aliphatic amideswhose composition is shown in the following table:

TABLE II 1 Time of Max. Solubility in- Ex. Reactants Catalyst reaction temp., Color and physical state No. (NaOOH=) (hrs.) 0.

Water 5% HOAO Xylene 1a--- Armeen 8D, 133 g. +B, 110 g No 1. 5 195 Brown semisolid 2a Armeen 12D, 104 g. +B, 55 g. N 1. 200 Raddish semis0lid D 3a- Armeen 16D, 126 g. +B, 55 g No 1. 5 200 Brown semisolid. 4a Armeen 18D, 138 g. No 1.5 200 Brown soft solid 5u Primene 81T, 108.5 N0 2 180 Dark brown SBH11S0lld. 6a- Primene .TM-T, 172 No 2 200 Reddish brown semisolid 7a- Rosin Amine D, 157. No 2 195 Reddish solid 8a- Duomeen 12, 151.5 g. N o 2 185 Dark brown semiso1id 9a--- Duomeen C, 160.5 g +B No 2 180 Dark semisolid d 10a. Duomeen T, 200 g. No 2 175 Brown semisolid d 11a Armid 14, 68.4 g. +3 1 2 200 Dark brown solid Partly dis- Partlyi l )i1is- D0.

pers e. 1202-- Armld 16, 77.4 g. +B, 1. 1 2 220 Brown solid Do. 13a Ethomeen 0/20, 64.6 g. +B, 11 g 0.8 1 200 Amber liquid. Do. 140.- Ethomeen 18/2 71.6 g. +B, 11 g 0.8 1 210 0 Do. 1511.. Ethonn'd HIl15, 79.6 g. +B, 17.6 g. 1 2. 5 220 Yellow solid Do.

1611.. Ethomid R0/25, 75.4 g. +B, 8.8 g 0. 9 2 210 Brownseinisolidl Soluble Do. 17a Fliriiirglafilgiisie+plrgpyllene oxide No 2 190 Dark brown liqui Dispersible -.do D0.

.g. 1g. v 1812.. Furiurylamine+propylene oxide N o 2 200 .do do .do D0.

1:51.8, 155 g. +B, 5.5 g. 'l9a Triethanolamine-l-propylene ox- No 2.5 200 .d0 .do -.do Do.

ide 1:27, 171.5 g. +B, 11 g. 2011.- Triethanolamine+propylene ox- N0 3 210 Brown liquid "do do Do.

ide 1:302, 190 g. +B, 11 g.

As has been pointed out previously, high molal amines, TABLE IV molal diammes of certain types and certain other products are commonly sold and identified by certain trade Carbon Armid Amid Amid Amid names simply as a matter of convenience. In the preehair i 10 14 16 HT vious tables such commonly used identifications have been lengt employed. In some instances evidently the same product id is now, or shortly will be, available from more than one m source. For this reason the following tables give more specific information as to certain of these products which r are referred to in the table, and other similar products H d c which are equally effective and may be used to compar- 33, 5 ,555; 70 able advantage. gillflgggelg. 5 As to the high molecular weight aliphatic primary Z ""jjjj amines described as Armeens, their composition 1s shown APPWX- meltmg W111i, by the following table:

TABLE III Carbon Armeen Armean Armeen Armeen Armeen Armeen Armeen Armeen Armeen Armeen chain 8 8D 10D 12 12D 14D 16 16D 18 18D length iii-Primary amine:

Tetra-decyl Hexadecyl 90 90 Octadecyl- 6 6 Octadeeenyl 4 4 Oetadeeadienyl Mean molecular weight of primary amine mutant 244 244 267 267 M01 combining weight percent primary 287 252 314 276 Percent primary amine by titration 85 97 85 97 Approx. melting point, C 38 38 55 As stated in the pamphlet distributed by Armour Chemical Division, Armour and Company, Chicago, Illinois, and entitled Ethomeens' Ethomids Ethofats, the Ethomeens are essentially oxyalkylated fatty primary amines of the type characterized by the Armeens previously described. If desired, any one of the previous Armeens can be treated with one to five times its weight of ethylene oxide and-thus obtain a series of compounds which will serve in the same manner as the Ethomeens employed in the examples of Table I.

The Ethomids are products obtained similarly from the high molal fatty primary amides such as the Arrnids previously described. These amides can be treated w ith ethylene oxide in the same weight ratio as above and obtain a seriesof compoundswhich are just assuitable for the reaction process as the Ethomeens described above 19 For further information on the Ethomids see the circular referred to previously in regard to the Ethomeens.

Rosin Amin'eD is the commercial amine obtained from rosin in the same manner that primary amines are obtained from higher fatty acids. It is a viscous liquid containing approximately 90% or more amine. Its color is pale yellow, it has a nitrogen content of 4.3 to 4.5 and a neutralization value of 312 to 322. It is furnished by at least one company, to wit, the Hercules Powder Company.

Previous reference has been made to the use of oxyethylated high molal weight fatty amides. Equally satisfactory are the products derived from Rosin Amine D. This is sold by the Hercules Powder Company under the designation Hercules Polyethanol Rosin Amine D." Typical examples are'the following:

Neutralization equivalent Percent Polyethanol rosin amine D products nitrogen PART 4 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and eifect to the instant process, noting only thatwhere reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 3a herein described.

Having thus described our invention, what we claim as new and desire to secure by LettersPatent is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction product of (A) a monomeric organic nonresinous nitrogen-containing compound having at least one reactive hydrogen atom, and (B) nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical H CE in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; .with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with theadded 20 proviso that the reaction product be a member of the class consisting of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction product of (A) a monomeric organic nonresinous nitrogen-containing compound having at least one reactive hydrogen atom, and (B) nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class consisting of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction product of (A) a monomeric organic nonresinous nitrogen-containing compound having at least one reactive hydrogen atom, and (B) nonaryl hydrophile diepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the diepoxide, is water-soluble; said diepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxide being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class consisting of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

4. A process for breaking petroleum emulsions of the atlases polyhydric alcohol, in which anoxygen-linked hydrogen atom is replaced subsequently by the radical in the diepoxide, is water-soluble; said diepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxide being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class consisting of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. The process of claim 4 wherein the diepoxide contains at least one reactive hydroxyl radical.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being the reaction product of (A) a monomeric organic nonresinous nitrogen-containing compound having at least one basic nitrogen atom and containing at least one reactive hydrogen atom, and (B) a hydroxylated diepoxypolyglycerol having not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class consisting of solvent-soluble liquids and lowmelting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

7. The process of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei.

8. The process of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the amine contains at least 2 basic nitrogen atoms.

9. The process of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the amine contains at least 2 basic nitrogen atoms and at least one radical having in excess of 8 carbon atoms.

10. The process of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, the amine contains at least 2 basic nitrogen atoms and at least one radical having in excess of 8 carbon atoms and not over 22 carbon atoms.

11. The process of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, the amine contains at least 2 basic nitrogen atoms and an aliphatic radical having at least 8 and not over 22 carbon atoms.

12. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution in. shaken vigorously with l to 3 volumes of water.

13. The process of claim 2 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xyf'lene solution is shaken vigorously with 1 to 3 volumes 0 water.

14. The processof c aim 3 with theproviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, is an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 5 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 6 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 7 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

19. The process of claim 8 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

20. The process of claim 9 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

21. The process of claim 10 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

22. The process of claim 11 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

(References on following page) 2,262,743 De Groote et a1 Nov. 11, 1941 3 24 References Cited in the file Qf this patent 1 2,292,208- De .Groote'et a1. Aug. 4, 1942 UNITED'STATE PATENTS 2,457,634 Bond DEC. 28, 1948' S 2,538,792 Moersch Ian. 23, 1951 2, D I e et a1 1941 2 541 0 9 Nikawitz b 13 1951 ,2 D 6t 1 1941 5 2 552 534 De Groom May 15 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILE PRODUCTS BEING THE REACTION PRODUCT OF (A) A MONOMERIC ORGANIC NONRESINOUS NITROGEN-CONTAINING COMPOUND HAVING AT LEAST ONE REACTIVE HYDROGEN ATOM, AND (B) NONARYL HYDROPHILE POLYEPOXIDES CHARACTERIZED BY THE FACT THAT THE PRECURSORY POLYHYDRIC ALCOHOL, IN WHICH AN OXYGEN-LINKED HYDROGEN ATOM IS REPLACED SUBSEQUENTLY BY THE RADICAL 